Mu-Rong Chao

Characteristics of polycyclic aromatic hydrocarbons and total suspended particulate in indoor and outdoor atmosphere of a Taiwanese temple.

Incense burning, a common and popular practice among many families and in most temples in Taiwan, can result in indoor pollution-related health problems. This exploratory study was aimed at characterizing human exposure to polycyclic aromatic hydrocarbons (PAHs) and total suspended particulate (TSP) inside and around a Taiwanese temple, and to compare the indoor levels with levels outside. Additionally, three types of commonly used unburned incense and incense ash were analyzed in order to evaluate the relationship between incense composition and PAH emissions.Standard methods were used to determine air concentrations of 21 PAHs and TSP inside and around a chosen temple. Indoor mean total-PAH concentration, particle-bound PAH concentration and TSP concentration were 6258 ng/m(3), 490 micro g/g and 1316 micro g/m(3), respectively; values for outdoor readings were 231 ng/m (3), 245 micro g/g and 73 micro g/m(3), for outdoors, respectively indicating PAH and TSP concentrations inside 27 and 18 times greater, respectively than outdoors. With respect to concentrations of individual PAHs (particulate+gas phase), the five highest concentrations were of acenaphthylene (AcPy) (3583 ng/m(3)), naphthalene (Nap) (1264 ng/m(3)), acenaphthene (Acp) (349 ng/m(3)), fluoranthene (FL) (243 ng/m(3)) and phenanthrene (PA) (181 ng/m(3)). Median values for indoor/outdoor (I/O) ratios of individual PAHs ranged from 5.7 to 387.9, which implied that the temple was a significant PAH source. Moreover, PAH content of the tested stick incense and ash was very low. PAH levels inside the temple were much higher than those measured in the vicinity and inside residential houses; and were in fact close to levels measured at a local traffic intersection in Tainan, Taiwan, and those in a graphite-electrode producing plant during the graphitization process. It is obvious that such substantially high concentrations of PAHs and TSP constitute a potential health hazard to people working in or visiting the temple.

Effects of methanol-containing additive on emission characteristics from a heavy-duty diesel engine

This study was aimed to investigate the effect of methanol-containing additive (MCA) on the regulated emissions of hydrocarbons (HC), carbon monoxide (CO), nitrogen oxides (NOx), particulate matter (PM), as well as the unregulated carbon dioxide (CO2) and polycyclic aromatic hydrocarbons (PAHs) from a diesel engine. The engine was tested on a series of diesel fuels blended with five additive levels (0, 5, 8, 10 and 15% of MCA by volume). Emissions tests were performed under both cold- and hot-start transient heavy-duty federal test procedure (HD-FTP) cycles and two selected steady-state modes. Results show that MCA addition slightly decreases PM emissions but generally increases both THC and CO emissions. Decrease in NOx emissions was found common in all MCA blends. As for unregulated emissions, CO2 emissions did not change significantly for all MCA blends, while vapor-phase and particle-associated PAHs emissions in high load and transient cycle tests were relatively low compared to the base diesel when either 5 or 8% MCA was used. This may be attributed to the lower PAHs levels in MCA blends. Finally, the particle-associated PAHs emissions also showed trends quite similar to that of the PM emissions in this study.

Effect of methanol-containing additive on the emission of carbonyl compounds from a heavy-duty diesel engine

This study was aimed at determining the effect of methanol-containing additive (MCA) on the emission of carbonyl compounds (CBCs) generated from the diesel engine. For this experiment, a heavy-duty diesel engine was connected with a full flow critical flow ventri (CFV) type dilution tunnel, a Schenck GS-350 DC dynamometer, and a DC-IV control system in series. The operating conditions of the heavy-duty diesel engine for both cold-start and hot-start Transient Cycle tests and for both low-load and high-load steady-state tests were ascertained. The exhaust of CBCs collected from a 2,4-dinitrophenylhydrazine (2,4-DNPH)-coated cartridge were first converted to corresponding hydrazone derivatives, which were then solvent-eluted and analyzed by a High Performance Liquid Chromatograph (HPLC) with an ultraviolet-visible (UV) detector. When either 10% or 15% MCA was used, the emission factors of the CBCs acrolein and isovaleraldehyde increased by at least 91%. Accordingly, future studies must be done to cut down the emission of CBCs when MCA and methanol alternative fuels are used.

Characterization of multiple airborne particulate metals in the surroundings of a municipal waste incinerator in Taiwan

Abstract Heavy metals are one of the concerned pollutants emitted by the municipal waste incineration system (MWIs). The objective of this study was to evaluate the potential impact on local airborne metals from the emissions of an MWI. Aerosol samples were simultaneously collected at eight different sites around the municipal waste incinerator using PS-1 sampler. The concentrations of 16 elements (Mg, Al, Fe, Cu, Zn, Pb, Ti, V, Cr, Mn, Co, Ni, As, Cd, Ba and Hg) were quantified by inductively coupled plasma-mass spectrometry (ICP–MS) and atomic absorption spectrometer (AA). The profiles of the 16 metals in the surroundings of a municipal incinerator in central Taiwan were compared with those of the emission sources. The results showed that the profiles of multiple metals obtained at all sampling sites were similar to those emitted from the MWI stack. These findings suggested that the local airborne metal pollutants might probably derive from the stack emission of the MWI. Using cadmium as an index metal, it was found that the metals like Mg, Ti, V, Cr, Mn, Co, Ni, As, and Hg are highly influenced by the stack emission from the municipal incinerator. Moreover, the ratio of other metals to Cd that were increased with the distance from the incinerator. This might be due to the additional sources contributed to airborne metals following the emission from the incinerator and a difference in particle size of each particle-bound metal.

Comparative syntheses of tetracycline-imprinted polymeric silicate and acrylate on CdTe quantum dots as fluorescent sensors.

The amphoteric drug molecule tetracycline, which contains groups with pKa 3.4-9.9, was used as a template for conjugating molecularly imprinted polymers (MIPs) and as a quencher for CdTe quantum dot (QD) fluorescence. Two MIP-QD composites were synthesized by a sol-gel method using a silicon-based monomer and a monomer linker between the MIP and QD, i.e., tetraethoxylsilane/3-mercaptopropyltriethoxysilane (MPS) and tetraethoxylsilane/3-aminopropyltriethoxysilane (APS). Another MIP-QD composite was synthesized by the chain-growth polymerization of methacrylic acid (MAA) and an allyl mercaptan linker. The prepared MIP-QDs were characterized by FTIR and SEM and utilized at 0.33 mg/mL to determine the tetracycline content in phosphate buffers (pH 7.4, 50mM) through the Perrin and Stern-Volmer models of quenching fluorometry. The Perrin model was applied to tetracycline concentrations of 7.4 μM-0.37 mM for MIP-MPS-QD, 7.4 μM-0.12 mM for MIP-APS-QD, and 7.4 μM-0.10mM for MIP-MAA-QD (R(2)=0.9988, 0.9978, and 0.9931, respectively). The Stern-Volmer model was applied to tetracycline concentrations of 0.12-0.37 mM for MIP-APS-QD (R(2)=0.9983) and 0.10-0.37 mM for MIP-MAA-QD (R(2)=0.9970). The detection limits were 0.45 μM, 0.54 μM, and 0.50 μM for MIP-MPS-QD, MIP-APS-QD, and MIP-MAA-QD, respectively. Equilibrium times, differences between imprinted and nonimprinted polymers, and MIP-QD quenching mechanisms were discussed. Finally, specificity studies demonstrated that MIP-MAA-QD exhibited optimal recoveries of 96% from bovine serum albumin (n=5, RSD=3.6%) and 91% from fetal bovine serum (n=5, RSD=4.8%).

Determination of urinary malondialdehyde by isotope dilution LC-MS/MS with automated solid-phase extraction A cautionary note on derivatization optimization

A highly sensitive quantitative LC-MS/MS method was developed for measuring urinary malondialdehyde (MDA). With the use of an isotope internal standard and online solid-phase extraction, urine samples can be directly analyzed within 10 min after 2,4-dinitrophenylhydrazine (DNPH) derivatization. The detection limit was estimated as 0.08 pmol. This method was further applied to assess the optimal addition of DNPH for derivatization and to measure urinary MDA in 80 coke oven emission (COE)-exposed and 67 nonexposed workers. Derivatization optimization revealed that to achieve complete derivatization reaction, an excess of DNPH is required (DNPH/MDA molar ratio: 893-8929) for urine samples that is about 100 times higher than that of MDA standard solutions (molar ratio: 10-80). Meanwhile, the mean urinary concentrations of MDA in COE-exposed workers were significantly higher than those in nonexposed workers (0.23±0.17 vs 0.14±0.05 μmol/mmol creatinine, P<0.005). Urinary MDA concentrations were also significantly associated with the COE (P<0.005) and smoking exposure (P<0.05). Taken together, this method is capable of routine high-throughput analysis and accurate quantification of MDA and would be useful for assessing the whole-body burden of oxidative stress. Our findings, however, raise the issue that derivatization optimization should be performed before it is put into routine biological analysis.

Repeated measurements of urinary methylated/oxidative DNA lesions, acute toxicity, and mutagenicity in coke oven workers

We conducted a repeated-measures cohort study of coke oven workers to evaluate the relationships between the traditional exposure biomarker, urinary 1-hydroxypyrene (1-OHP), and a series of biomarkers, including urinary 8-oxo-7,8-dihydro-2′-deoxyguanosine (8-oxodG), N7-methylguanine (N7-MeG), acute toxicity, and mutagenicity. A total of eight spot urine samples were collected from each high-exposed (at topside oven area) and low-exposed workers (at side oven area) during the whole working cycle, which consisted of 6 consecutive days of working followed by 2 days off. Our results showed that the high-exposed workers had significantly higher urinary levels of 1-OHP, 8-oxodG, and N7-MeG compared with the low-exposed workers. Acute toxicity and mutagenicity of urine were also found to be markedly increased in the high-exposed workers, as determined by Microtox assay and Ames test, respectively. Multivariate regressions analysis revealed that the urinary 8-oxodG, N7-MeG, or acute toxicity was significantly correlated with 1-OHP concentrations. Overall, the present study showed that exposure to coke oven emissions increased oxidatively damaged DNA products and mutagenicity of urine, and for the very first time, such exposure was also found to increase DNA methylation and urinary acute toxicity. The potential source of methylating agents in coke oven emissions warrants further investigation. Additionally, with repeated measurements, the pattern of time course for urinary 1-OHP was found to be different from those of 8-oxodG and N7-MeG, as well as acute toxicity and mutagenicity. This finding implies that the single measurement that was often conducted in occupational healthy investigations should be used with certain precautions, because single measurement may fail to provide the proper information of interest. (Cancer Epidemiol Biomarkers Prev 2008;17(12):3381–9)

Assessing the influence of methanol-containing additive on biological characteristics of diesel exhaust emissions using microtox and mutatox assays

Here we investigate the effect of the methanol-containing additive (MCA) on the biological characteristics of diesel exhaust emissions. Microtox and Mutatox assays, respectively, were used to evaluate the acute toxicity and genotoxicity of crude extracts from diesel engine exhaust. The engine was tested on a series of diesel fuels blended with five additive levels (0, 5, 8, 10 and 15% of MCA by volume). Emission tests were performed over the hot start portion of the transient Heavy-Duty-Federal Test Procedure (HD-FTP) and two selected steady-state modes. Microtox results show that MCA additive moderately lowers the toxicity levels of particle-associated (SOF) samples, but generally increase the vapor-phase (XOC) associated toxicity. A strong correlation was found between XOC-associated toxicity and total hydrocarbon (THC) concentrations, while only a slight link was found between SOF-associated toxicity and particulate matter (PM) concentrations. For Mutatox test results, when either 5 or 8% MCA used, XOC and SOF-associated genotoxicity in both steady-state and hot-start transient cycle tests were relatively lower compared to those of the base diesel. The genotoxic potential of XOC samples was significantly increased after treatment with an exogenous metabolic activation system (S9). On the contrary, the genotoxic potential of SOF samples without S9 metabolic activation was generally higher than those with S9. It is noteworthy that the total particle-associated (SOF) PAHs emissions showed trends quite similar to that of the genotoxic potential. As expected, the total particle-associated (SOF) PAHs correlated moderately with direct mutagenicity, and fairly well with indirect mutagenicity. Finally, the genotoxicity data did not parallel the Microtox results in this study, indicating that potentially long-term genotoxic agents may not be revealed by short-term toxicity assays.

Hydrophilic ionic liquid-passivated CdTe quantum dots for mercury iondetection

A hydrophilic ionic liquid, 1-ethyl-3-methylimidazolium dicyanamide (EMIDCA), was used as a medium for the synthesis of highly luminescent CdTe nanocrystals (NCs) capped with thioglycolic acid (TGA). The synthesis was performed for 8 h at 130 °C, was similar to nanocrystal preparation in an aqueous medium, and used safe, low-cost inorganic salts as precursors. After the reaction, the photoluminescence quantum yield of the CdTe NCs (NC(IL-130)) prepared in EMIDCA was significantly higher than that of the nanocrystals prepared in water (NC(w)) at 100 °C (86% vs. 35%). Moreover, the emission wavelength and particle size of NC(IL-130) were smaller than NC(w) (450 nm vs. 540 nm and 4.0 nm vs. 5.2 nm, respectively). The activation of NC(IL-130) was successful due to the coordinated action of two ligands, EMIDCA and TGA, in the primary steps of the NC formation pathway. An increase or decrease in the synthesis temperature, to 160 °C or 100 °C, respectively, was detrimental to the luminescence quality. However, the quenching effect of Hg²⁺ on the fluorescence signals of the NC(IL-130) was distinctively unique, whereas certain interfering ions, such as Pb²⁺, Fe³⁺, Co²⁺, Ni²⁺, Ag⁺, and Cu²⁺, could also quench the emission of the NC(w). Based on the Perrin model, the quenching signals of NC(w) and NC(IL-130) were well correlated with the Hg²⁺ concentrations in the phosphate buffer (pH 7.5, 50 mM). In comparison with the NC(w), the NC(IL-130) had a high tolerance of the interfering ions coexisting with the Hg²⁺ analyte, high recovery of Hg²⁺ spiked in the BSA- or FBS-containing medium, and high stability of fluorescence quenching signals between trials and days. The NC(IL-130) nanocrystals can potentially be used to develop a probe system for the determination of Hg²⁺ in physiological samples.

Simultaneous determination of N7-alkylguanines in DNA by isotope-dilution LC-tandem MS coupled with automated solid-phase extraction and its application to a small fish model

In the present study, we report the development of a sensitive and selective assay based on LC (liquid chromatography)-MS/MS (tandem MS) to simultaneously measure N7-MeG (N7-methylguanine) and N7-EtG (N7-ethylguanine) in DNA hydrolysates. With the use of isotope internal standards (15N5-N7-MeG and 15N5-N7-EtG) and on-line SPE (solid-phase extraction), the detection limit of this method was estimated as 0.42 fmol and 0.17 fmol for N7-MeG and N7-EtG respectively. The high sensitivity achieved here makes this method applicable to small experimental animals. This method was applied to measure N7-alkylguanines in liver DNA from mosquito fish (Gambusia affinis) that were exposed to NDMA (N-nitrosodimethylamine) and NDEA (N-nitrosodiethylamine) alone or their combination over a wide range of concentrations (1-100 mg/l). Results showed that the background level of N7-MeG in liver of control fish was 7.89+/-1.38 mmol/mol of guanine, while N7-EtG was detectable in most of the control fish with a range of 0.05-0.19 mmol/mol of guanine. N7-MeG and N7-EtG were significantly induced by NDMA and NDEA respectively, at a concentration as low as 1 mg/l and increased in a dose-dependent manner. Taken together, this LC-MS/MS assay provides the sensitivity and high throughput required to evaluate the extent of alkylated DNA lesions in small animal models of cancer induced by alkylating agents.